WO2023137262A1 - Systèmes et procédés de régénération d'alliage de cuivre - Google Patents

Systèmes et procédés de régénération d'alliage de cuivre Download PDF

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WO2023137262A1
WO2023137262A1 PCT/US2023/060337 US2023060337W WO2023137262A1 WO 2023137262 A1 WO2023137262 A1 WO 2023137262A1 US 2023060337 W US2023060337 W US 2023060337W WO 2023137262 A1 WO2023137262 A1 WO 2023137262A1
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copper alloy
alloy powder
powder particles
recycled
particles
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PCT/US2023/060337
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English (en)
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Azin Houshmand
John Meyer
Makhlouf Redjdal
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6K Inc.
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Publication of WO2023137262A1 publication Critical patent/WO2023137262A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/06—Metallic powder characterised by the shape of the particles
    • B22F1/065—Spherical particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/14—Treatment of metallic powder
    • B22F1/142—Thermal or thermo-mechanical treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/70—Recycling
    • B22F10/73—Recycling of powder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F8/00—Manufacture of articles from scrap or waste metal particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
    • B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0425—Copper-based alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F2009/001—Making metallic powder or suspensions thereof from scrap particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2201/00—Treatment under specific atmosphere
    • B22F2201/01—Reducing atmosphere
    • B22F2201/013—Hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2201/00—Treatment under specific atmosphere
    • B22F2201/10—Inert gases
    • B22F2201/11—Argon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2202/00—Treatment under specific physical conditions
    • B22F2202/13—Use of plasma
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/10—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2304/00—Physical aspects of the powder
    • B22F2304/10—Micron size particles, i.e. above 1 micrometer up to 500 micrometer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/25—Process efficiency

Definitions

  • the present disclosure is generally directed in some embodiments to producing spheroidal powder products from feedstock materials generated from recycled used and/or high interstitial content powder.
  • AM additive manufacturing
  • L-PBF laser powder bed fusion
  • GRCop-42 is a high conductivity, high-strength dispersion strengthened copper-alloy (Cu-alloy) for use in high heat flux applications such as liquid rocket engine combustion devices.
  • GRCop-42 alloy is part of the family of copper-chromium- niobium alloys. GRCop alloys were developed to be utilized in harsh environments specific to regeneratively-cooled combustion chambers and nozzles with good oxidation resistance. Processes for additive manufacturing using GRCop-42 have been developed, specifically laser powder bed fusion (L-PBF). GRCop-42 has several advantages over other copper-chromium- niobium alloys, including higher conductivity, faster build speeds, and a simplified powder supply chain.
  • L-PBF laser powder bed fusion
  • Some embodiments herein are directed to methods for manufacturing recycled copper alloy powder particles from used copper alloy powder particles, the method comprising: introducing used or deficient copper alloy powder particles into a microwave plasma torch, the used copper alloy powder particles comprising an oxygen content above 600 ppm by weight; and heating the used or deficient copper alloy powder particles within the microwave plasma torch to form recycled copper alloy powder particles, the recycled copper alloy powder particles comprising a reduced oxygen content relative to the used or deficient copper alloy.
  • the recycled copper alloy powder has an oxygen content at or below 600 ppm by weight.
  • the used or deficient copper alloy powder particles and the recycled copper alloy powder particles comprise a GRCop (Cu- CnNb) family alloy.
  • the GRCop family alloy comprises GRCop-42.
  • the methods further comprise collecting the used or deficient copper alloy powder particles from an additive manufacturing process.
  • the used or deficient powder particles comprise an oxygen content above 1000 ppm by weight.
  • the recycled copper alloy powder particles comprise an oxygen content at or below 500 ppm by weight.
  • the used or deficient copper alloy powder particles are heated to a temperature sufficient to remove oxygen from a surface and/or sub-surface of the used copper alloy powder particles. In some embodiments, the used or deficient copper alloy powder particles are heated to a temperature of less than 1,100 °C.
  • a reducing gas is introduced into the microwave plasma torch to generate a microwave plasma that heats the used or deficient copper alloy powder particles within the microwave plasma torch.
  • the reducing gas is hydrogen gas (H2).
  • the hydrogen gas is mixed with argon gas.
  • the hydrogen gas reacts with the used powder particles to reduce the oxygen.
  • the recycled copper alloy powder particles have a median sphericity of at least 0.950. In some embodiments, the recycled copper alloy powder particles have a D50 of about 15 pm to about 45 pm. In some embodiments, the recycled copper alloy powder particles comprise a substantially homogenous microstructure.
  • Some embodiments herein are directed to recycled copper alloy particles manufactured by a process comprising: introducing used or deficient copper alloy powder particles into a microwave plasma torch, the used or deficient copper alloy powder particles comprising an oxygen content above 600 ppm by weight; and heating the used copper alloy powder particles within the microwave plasma torch to form recycled copper alloy powder particles, the recycled copper alloy powder particles comprising a reduced oxygen content relative to the used or deficient copper alloy.
  • the recycled copper alloy powder has an oxygen content at or below 600 ppm by weight.
  • the recycled copper alloy powder particles have a median sphericity of at least 0.950.
  • the recycled copper alloy powder particles have a D50 of about 15 pm to about 45 pm.
  • the recycled copper alloy powder particles comprise a substantially homogenous microstructure.
  • the used or deficient copper alloy powder particles and the recycled copper alloy powder particles comprise a GRCop family alloy.
  • the GRCop (Cu-CnNb) family alloy comprises GRCop-42.
  • FIG. 1 illustrates an exemplary microwave plasma torch that can be used in the production of Cu-alloy materials, according to embodiments of the present disclosure.
  • FIGS. 2A-B illustrates an exemplary microwave plasma torch that can be used in the production of Cu-alloy materials, according to embodiments of the present disclosure.
  • FIG. 3 illustrates a table comparing properties of an example used powder and a recycled Cu-alloy powder processed according to some embodiments described herein.
  • FIG. 4 illustrates a microscopic image comparing example used particles and a recycled Cu-alloy powder processed according to some embodiments described herein.
  • FIG. 5 illustrates cross-sectional back-scattered electron detector (BSE) images comparing example used particles and a recycled Cu-alloy powder processed according to some embodiments described herein.
  • BSE back-scattered electron detector
  • FIG. 6 illustrates an example x-ray powder diffraction (XRD) plot comparing example used particles and a recycled Cu-alloy powder processed according to some embodiments described herein.
  • XRD x-ray powder diffraction
  • Some embodiments herein are directed to recycling used Cu-alloy powders, including Cu-alloys in the GRCop family, and particularly, GRCop-42.
  • GRCop is a preferred material family for use in rocket engine combustion chamber liners due to oxidation and blanching resistance with thermal and oxidation-reduction cycling, high use temperatures to above approximately 800°C for sustained durations, material strength at high use temperatures, an established powder supply chain, and a mature AM process.
  • the CnNb dispersoids have extreme temperature stability up until 800°C, making them exceptional high temperature strengtheners (above this temperature dispersoids begin to coarsen).
  • GRCop powder can be consolidated through direct extrusion or hot isostatic pressing of bulk powder, resulting in a fully dense solid form that can then be machined and worked as any copper alloy. Otherwise, for powder bed applications, the consolidation can be avoided.
  • GRCop-42 (Cu - 4 at. % Cr - 2 at. % Nb) in particular shows improvement in conductivity over other GRCop-alloys, limited reduction in strength compared to GRCop-84, and exhibits simplified powder atomization over GRCop-84.
  • GRCop-42 trades lower mechanical properties such as strength for significantly higher thermal conductivity.
  • GRCop-42 achieves 85% of the International Annealed Copper Standard (IACS) versus 75% IACS for GRCop-84 at room temperature.
  • IACS International Annealed Copper Standard
  • GRCop-42 has greatly improved thermal conductivity compared GRCop-84 and competing alloys, while having the same strengthening mechanism as GRCop-84, and nearly identical strength up to about 800°C, making it significantly higher than current launch vehicle engine liners.
  • thermal conductivity is needed to minimize both the hot wall temperature and thermal gradient through the liner wall.
  • LCF occurs during repeated hot firings of the engine during qualification and flight.
  • thermal expansion of the constrained liner causes a deformation of 1% or more. This can result in a rapid degradation of the liner and ultimately failure.
  • GRCop-42 Based on the development work with extruded GRCop-42, it was determined it could meet several requirements, including high thermal conductivity, excellent creep resistance, long low-cycle fatigue life, and good strength at elevated temperatures. As such, AM processes have been and continue to be developed to build GRCop-42 parts for rocket engine combustion chamber liners.
  • rejuvenation or recycling comprises reducing/removing oxygen, cleaning the surface, and regenerating the powder particles within alloy specifications.
  • the embodiments herein enable the rejuvenation of old or used feedstock powder, including used Cu-alloy powder, which does not meet alloy specifications for AM, mainly due to high oxygen content, as a result of oxidation during production, storage, or use.
  • the plasma processing described herein can be applied to powders with high oxygen content to produce powders with lower oxygen content and higher sphericity ideal for additive manufacturing applications.
  • old or used powder may be used interchangeably and may refer to powder that was previously used in an AM process prior to receiving the powder, but also to, for example, powder that had not been used previously, but had been oxidized prior to any use.
  • old or used powder may comprise material produced by an atomizer that is out of specification for use by, for example, an AM process.
  • Deficient” powder may also be used to describe the same materials, including those materials that have high interstitial content, low flowability, or low sphericity due to initial production or storage prior to AM or HIP use.
  • rejuvenated or recycled Cu-alloy powder particles should exhibit a spherical shape, which can be achieved through the process of spheroidization.
  • This process involves introducing the particles into a plasma processing apparatus with an inert gas (e.g., Ar) and a reducing (e.g., H2) plasma.
  • the plasma processing may comprise a hot environment, whereby the process cleans the surface of the particles and strip oxygen in presence of reducing gas.
  • the temperature may be maintained at a temperature sufficient to clean the surface and/or near-surface bulk, but not high enough to fully re-melt the particles.
  • the plasma processing process may comprise heating used powder particles to a temperature of less than about l,100°C, less than about l,000°C, less than about 900°C, less than about 800°C, less than about 700°C, or less than about 600°C, less than about 500°C, or any value between the aforementioned values.
  • H2 may be used as a reductive gas, reacting with the surface of the metal, which may be covered with a metal oxide.
  • the H2 may react with the surface oxide reduce the surface oxide to its native metal.
  • oxygen may be removed from the surface and/or near-surface and the resulting processed powder may have a lower oxygen content relative to the used metal powder.
  • each particle may be re-shaped into a spherical geometry, followed by cooling.
  • the outer region of an induction plasma can reach about 10,000 K while the inside processing region may only reach about 1,000 K.
  • This large temperature difference leads to processing and feeding problems.
  • induction plasma apparatuses are unable to process materials at a low enough temperature to avoid melting of certain materials, including GRCop alloys, without extinguishing the plasma.
  • the microwave plasma methods and systems described herein may overcome the problems with existing powder recycling technologies by processing used copper alloys.
  • the embodiments herein provide a new method to recycle Cu alloys by reducing oxygen without the need to fully melt the particles.
  • avoiding melting the particles may be critical, as melting results in coarsening and heterogeneity of the microstructure, as low density intermetallic may migrate to the particle surface.
  • controlling the process to avoid melting allows reduction of the surface oxide to the native metal without altering the composition and microstructure in the core of the particle.
  • the processes described herein avoid volatilization of the various elements that would affect chemistry/phase balance of the resulting powder.
  • the plasma processing may avoid sintering of powder particles and improve sphericity, which results in improved powder flow.
  • the apparent density of the particles may be such that the powder is desirable for use in AM applications, such as laser powder bed fusion applications.
  • a microwave plasma process may be utilized to recycle/rejuvenate used Cu-alloy powder to improve sphericity, maintain alloy chemistry, limit/phase microstructural changes, and maximize oxygen reduction.
  • the recycled/rejuvenated powder may comprise oxygen at less than about 600 wt. ppm, and preferably less than about 500 wt. ppm. In some embodiments, the recycled/rejuvenated powder may comprise oxygen at about 0 wt. ppm to about 600 wt. ppm. For example, the recycled/rejuvenated powder may comprise oxygen at about 0 wt. ppm, less than about 100 wt. ppm, less than about 200 wt. ppm, less than about 300 wt. ppm, less than about 400 wt. ppm, less than about 500 wt. ppm, less than about 600 wt. ppm or any value between the aforementioned values.
  • the embodiments herein are primarily directed to recycling copper alloy powders, and in particular, alloys of the GRCop family, the disclosure herein is not limited to those materials.
  • the methods and systems herein may be applicable to any metal or metal alloy, with particular applicability to oxidized metal or metal alloys.
  • used powders comprising Pure Cu (e.g., Cl 10), Cu-Cr-Nb (e.g., GrCop42, GrCop84), Cu-Cr (e.g., C182/C18200), Cu-Cr-Zr (e.g., C18150), Cu-Be (e.g., Alloy 25 / C 17200, M25, 165), C11-AI2O3 (e.g., Glidcop) may be recycled/rejuvenated according to the methods described herein.
  • Pure Cu e.g., Cl 10
  • Cu-Cr-Nb e.g., GrCop42, GrCop84
  • Cu-Cr e.g., C182/C18200
  • Cu-Cr-Zr e.g., C18150
  • Cu-Be e.g., Alloy 25 / C 17200, M25, 165
  • C11-AI2O3 e.g., Glidcop
  • embodiments of methods, systems, devices, and assemblies for recycling/reusing/reconditioning used Cu-alloy powders e.g., out-of-spec powder, waste byproducts of AM processes, etc.
  • used Cu-alloy powders e.g., out-of-spec powder, waste byproducts of AM processes, etc.
  • embodiments of the disclosure allow for the taking of used Cu-alloy powder and converting it into a feedstock for a microwave plasma process to form a final spheroidized and oxygen-free powders, which is of sufficient quality to be used in different processes, such as additive manufacturing processes, metal injection molding (MIM), or hot isostatic pressing (HIP) processes.
  • MIM metal injection molding
  • HIP hot isostatic pressing
  • Used Cu-alloy powder can be of differing quality and therefore it can be challenging to make use of used Cu-alloy powder as feedstock for an AM process, which requires powder having precise specifications. Used Cu-alloy can be contaminated or an incorrect size, or altogether difficult or impossible to process.
  • the used Cu-alloy powders may be pre-processed before they are introduced into the plasma process.
  • the powders may be sieved to remove large agglomerations and selected the desired size to be processed in the plasma.
  • the powders may be cleaned with water, surfactant, detergent, solvent, or any other chemical such as acids to remove contamination.
  • the powders may be magnetically cleaned if they are contaminated with any magnetic material.
  • the powder can be pre-treated to de-oxidize the powder.
  • other elements or compounds can be added to compensate or modify the chemistry of the powder.
  • the powder can be de-dusted to remove fines.
  • the previously used powder can be modified to make it more applicable as the feedstock as the previous processing can make the powder/particles unusable.
  • “satellites,” which can hurt/reduce flow can be removed.
  • used powder can become agglomerated, and the disclosed process can separate the particles in the powder.
  • contaminants, such as organics can be removed.
  • carbon, nitrogen, oxygen, and hydrogen can be removed from the previously used powder by the disclosed process.
  • artifacts can be removed.
  • the disclosed process can also improve the flowability of the used powders.
  • surface texture can be adjusted to reduce surface roughness of used powder to improve flowability.
  • flowability can be improved by absorbing satellites.
  • residence time and power levels of a microwave plasma can be modified to absorb satellites or evaporate them, such as with minimal affect the chemistry of the bulk Cu-alloy powders.
  • embodiments of the disclosed methods can re- spheroidize the used Cu-alloy powers, for example a powder having particles that were spherical and have lost sphericity during a previous process, such as AM.
  • a previous process such as AM.
  • these previous processes can include, but are not limited to, to laser powder bed fusion (L-PBF), electron-beam powder bed fusion (EB- PBF), directed energy deposition (DED), and binder jetting.
  • the used powder can be larger powder waste from an electron beam process, which can then be made into a smaller powder for laser application.
  • the powder after use, has agglomerations, increased oxygen content, contamination from soot and inorganic materials, and/or deformation which makes them non-spherical.
  • the Cu-alloy powders cannot be reused without processing.
  • particle size distribution (PSD) of used powder particles and of recycled/rejuvenated particles comprises a minimum diameter (i.e., D10) of 12 micrometers (pm) and a maximum diameter (i.e., D90) of 42 pm, or a minimum of 5 pm and a maximum of 15 pm, or a minimum of 5 pm and a maximum of 23 pm, or a maximum of 23 pm, or a minimum of 15 pm and a maximum of 45 pm or a minimum of 22 pm and a maximum of 45 pm, or a minimum of 20 pm to a maximum of 63 pm, or a minimum of 45 pm and a maximum of 70 pm, or a minimum of 70 pm and a maximum of 106 pm, or a minimum of 105 pm to a maximum of 150 pm, or a minimum of 106 pm and a maximum of 300 pm, or other standard sizes per AMS7025 such as 0-23, or 0-45, or 5-45, or 10-45, or 15- 45, or 20-45, or 0-0
  • the disclosed processing methods retains alloy elements especially highly volatile elements such as Al, Cr, and Cu from the used powder.
  • This disclosure describes the rejuvenation of used Cu-alloy powders described above to produce recycled/rejuvenated powders with improved specifications sufficient for AM processing.
  • a microwave plasma process comprising exposing used Cu-alloy powders to microwave generated plasma is used to rejuvenate used powders described above to better specifications, such that they can be used again as feedstock to the AM, near net shape (NNS) HIP, or HIP + extrusion processes described above.
  • the particle size distribution can be maintained.
  • the particle size distribution can be improved/tightened by absorbing satellites.
  • the particle size distribution can be improved/tightened by re- spheroidizing large agglomerates.
  • used powder can include a) 5% by weight of satellites that are absorbed or evaporated by the microwave plasma process, and b) large misshapen agglomerations, both of which can be removed by embodiments of the disclosed process.
  • the particle size distribution can be the D50 of the particles in the powder.
  • the plasma gases can be specific to the materials of the powders.
  • a reducing gas such as H2
  • H2 may be used as a plasma gas to remove oxygen from the Cu-alloy particle.
  • an inert gas such as argon
  • the processed powder may not be chemically altered, besides the removal of oxygen.
  • using a noble gas with hydrogen gas may increase the uniformity of the plasma.
  • noble gases and mixtures such as argon a and argon/hydrogen mixtures are used to avoid any additional reaction between the powders and the plasma gases.
  • the recycling/reju venation of the used powder/particles can include the removal of artifacts, such as from an AM process. Further, satellites and agglomerated materials due to overheating, for example from a laser process outside a build line, can be removed.
  • the particular process to form the used particles such as additive processes, powder bed fusion, and binder jetting, is not limiting and other processes could have been performed on the original particles.
  • the recycling/rejuvenation of the used powder/particles can allow the powder/particles to, in some embodiments, regain their original rheological properties (such as bulk density, flowability, etc.).
  • the recycling/rejuvenation of used powder/particles can also improve the rheological properties. This can be achieved through the removing of any satellite on the surface through surface melting of the satellites and their incorporation into the bulk of the particle. In some cases, partial melting of the particles may densify particles and remove porosity. Also, in some embodiments, spheroidizing the powders increases their flowability.
  • a satellite may comprise a main powder particle that has a size that is within the defined particle size distribution to which a small particle of much smaller diameter that is outside the particle size distribution than the diameter of the main particle is agglomerated either through sintering or other physical processes.
  • An agglomeration can be two or more particles which coalesce to form a larger particle.
  • the recycling/reju venation can minimize oxygen content in the recycled powder. This can be achieved by, for example, adding hydrogen or another reducing agent, running in a closed environment, or running at a high temperature. In some embodiments, atmospheric pressure inert gas can be used. In some embodiments, a low oxygen environment can be used. In some embodiments, the alloying component chemistry or minor component chemistry may not be altered. In some embodiments, certain elements with low melting temperatures may be removed from the powder.
  • FIG. 1 illustrates an exemplary microwave plasma torch that can be used in the production of Cu-alloy materials, according to embodiments of the present disclosure.
  • Feed materials 9, 10 comprising used Cu-alloy particles can be introduced into a microwave plasma torch 2 in an introduction zone 3, the torch sustaining a microwave-generated plasma 11.
  • an entrainment gas flow, and a sheath flow may be injected through inlets 5 to create flow conditions within the plasma torch 2 prior to ignition of the plasma 11 via micro wave radiation source 1.
  • the entrainment flow and sheath flow are both axis- symmetric and laminar, while in other embodiments the gas flows are swirling.
  • the feed materials 9 are introduced axially into the microwave plasma torch 2, where they are entrained by a gas flow that directs the materials toward the plasma hot zone 6.
  • the gas flows can consist of a noble gas column of the periodic table, such as helium, neon, argon, etc.
  • the feed materials are melted in order to spheroidize the materials.
  • Inlets 5 can be used to introduce process gases to entrain and accelerate particles 9, 10 along axis 12 towards plasma 11.
  • particles 9 are accelerated by entrainment using a core laminar gas flow (upper set of arrows) created through an annular gap within the plasma torch.
  • a second laminar flow (lower set of arrows) can be created through a second annular gap to provide laminar sheathing for the inside wall of dielectric torch to protect it from melting due to heat radiation from plasma 11.
  • the laminar flows direct particles 9, 10 toward the plasma 11 along a path as close as possible to axis 12, exposing them to a substantially uniform temperature within the plasma.
  • suitable flow conditions are present to keep particles 10 from reaching the inner wall of the plasma torch 2 where plasma attachment could take place.
  • Particles 9, 10 are guided by the gas flows towards microwave plasma 11 were each undergoes homogeneous thermal treatment.
  • Various parameters of the microwave-generated plasma, as well as particle parameters, may be adjusted in order to achieve desired results. These parameters may include microwave power, feed material size, feed material insertion rate, gas flow rates, plasma temperature, residence time and cooling rates.
  • the cooling or quenching rate is not less than 10 +3 degrees C/sec upon exiting plasma 11.
  • the gas flows are laminar; however, in alternative embodiments, swirl flows or turbulent flows may be used to direct the feed materials toward the plasma.
  • FIGS. 2A-B illustrates an exemplary microwave plasma torch that includes a side feeding hopper rather than the top feeding hopper shown in the embodiment of FIG. 1, thus allowing for downstream feeding.
  • the feedstock is injected after the microwave plasma torch applicator for processing in the “plume” or “exhaust” of the microwave plasma torch.
  • the plasma of the microwave plasma torch is engaged at the exit end of the plasma torch to allow downstream feeding of the feedstock, as opposed to the top-feeding (or upstream feeding) discussed with respect to FIG. 1.
  • This downstream feeding can advantageously extend the lifetime of the torch as the hot zone is preserved indefinitely from any material deposits on the walls of the hot zone liner.
  • the downstream spheroidization method can utilize two main hardware configurations to establish a stable plasma plume which are: annular torch, such as described in U.S. Pat. Pub. No. 2018/0297122, or swirl torches described in US 8748785 B2 and US 9932673 B2.
  • annular torch such as described in U.S. Pat. Pub. No. 2018/0297122
  • swirl torches described in US 8748785 B2 and US 9932673 B2.
  • a feed system close-coupled with the plasma plume at the exit of the plasma torch is used to feed powder axis-symmetrically to preserve process homogeneity.
  • Other feeding configurations may include one or several individual feeding nozzles surrounding the plasma plume.
  • the feedstock powder can enter the plasma at a point from any direction and can be fed in from any direction, 360° around the plasma, into the point within the plasma.
  • the feedstock powder can enter the plasma at a specific position along the length of the plasma plume where a specific temperature has been measured and a residence time estimated for sufficient melting of the particles.
  • the feed materials 314 can be introduced into a microwave plasma torch 302.
  • a hopper 306 can be used to store the feed material 314 before feeding the feed material 314 into the microwave plasma torch 302, plume, or exhaust.
  • the feed material 314 can be injected at any angle to the longitudinal direction of the plasma torch 302. 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, or 55 degrees.
  • the feedstock can be injected an angle of greater than 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, or 55 degrees.
  • the feedstock can be injected an angle of less than 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, or 55 degrees.
  • the feedstock can be injected along the longitudinal axis of the plasma torch.
  • the microwave radiation can be brought into the plasma torch through a waveguide 304.
  • the feed material 314 is fed into a plasma chamber 310 and is placed into contact with the plasma generated by the plasma torch 302. When in contact with the plasma, plasma plume, or plasma exhaust, the feed material melts. While still in the plasma chamber 310, the feed material 314 cools and solidifies before being collected into a container 312. Alternatively, the feed material 314 can exit the plasma chamber 310 while still in a melted phase to cool and solidify outside the plasma chamber.
  • a quenching chamber may be used, which may or may not use positive pressure. While described separately from FIG. 1, the embodiments of FIGS. 2A and 2B are understood to use similar features and conditions to the embodiment of FIG. 1.
  • the recycled powders particles achieved by the plasma processing can be spherical or spheroidal, terms that can be used interchangeably.
  • Embodiments of the present disclosure are directed to producing particles that are substantially spherical or spheroidal or have undergone significant spheroidization.
  • spherical, spheroidal or spheroidized particles refer to particles having a sphericity greater than a certain threshold.
  • particles can have a sphericity (also referred to herein as sphericity factor) of greater than 0.5, 0.6, 0.7, 0.75, 0.8, 0.9, 0.91, 0.95, or 0.99 (or greater than about 0.5, about 0.6, about 0.7, about 0.75, about 0.8, about 0.8, about 0.91, about 0.95, or about 0.99). In some embodiments, particles can have a sphericity of 0.75 or greater or 0.91 or greater (or about 0.75 or greater or about 0.91 or greater).
  • particles can have a sphericity of less than 0.5, 0.6, 0.7, 0.75, 0.8, 0.9, 0.91, 0.95, or 0.99 (or less than about 0.5, about 0.6, about 0.7, about 0.75, about 0.8, about 0.8, about 0.91, about 0.95, or about 0.99).
  • a particle is considered to be spherical, spheroidal or spheroidized if it has a sphericity at or above any of the aforementioned sphericity values, and in some preferred embodiments, a particle is considered to be spherical if its sphericity is at or about 0.75 or greater or at or about 0.91 or greater.
  • a median sphericity of all particles within a given powder can be greater than 0.5, 0.6, 0.7, 0.75, 0.8, 0.9, 0.91, 0.95, or 0.99 (or greater than about 0.5, about 0.6, about 0.7, about 0.75, about 0.8, about 0.8, about 0.91, about 0.95, or about 0.99). In some embodiments, a median sphericity of all particles within a given powder can be less than 0.5, 0.6, 0.7, 0.75, 0.8, 0.9, 0.91, 0.95, or 0.99 (or less than about 0.5, about 0.6, about 0.7, about 0.75, about 0.8, about 0.8, about 0.91, about 0.95, or about 0.99).
  • a powder is considered to be spheroidized if all or a threshold percentage (as described by any of the fractions below) of the particles measured for the given powder have a median sphericity greater than or equal to any of the aforementioned sphericity values, and in some preferred embodiments, a powder is considered to be spheroidized if all or a threshold percentage of the particles have a median sphericity at or about 0.75 or greater or at or about 0.91 or greater.
  • the fraction of particles within a powder that can be above a given sphericity threshold can be greater than 50%, 60%, 70%, 80%, 90%, 95%, or 99% (or greater than about 50%, about 60%, about 70%, about 80%, about 90%, about 95%, or about 99%). In some embodiments, the fraction of particles within a powder that can be above a given sphericity threshold, such as described above, can be less than 50%, 60%, 70%, 80%, 90%, 95%, or 99% (or less than about 50%, about 60%, about 70%, about 80%, about 90%, about 95%, or about 99%).
  • Particle size distribution and sphericity may be determined by any suitable known technique such as by SEM, optical microscopy, dynamic light scattering, laser diffraction, manual measurement of dimensions using an image analysis software, for example from about 15-30 measures per image over at least three images of the same material section or sample, and any other techniques.
  • FIG. 3 illustrates a table comparing properties of an example used powder and a recycled Cu-alloy powder processed according to some embodiments described herein.
  • microwave plasma processing of the used powder in th plasma gas and argon resulted in improved sphericity, tap density and flowability in the recycled Cu-alloy powder.
  • the PSD was not significantly changed between the example used powder and the recycled Cu-alloy powder, although the PSD may optionally be altered during the plasma processing or using pre- or post-processing.
  • the composition of the powder was not significantly changed in the final recycled Cu-alloy powder.
  • the oxygen wt. ppm was significantly reduced in the recycled Cu-alloy powder (600 wt. ppm) relative to the used powder (1,090 wt. ppm).
  • FIG. 4 illustrates a microscopic image comparing example used particles and a recycled Cu-alloy powder processed according to some embodiments described herein.
  • the microwave-plasma processed recycled Cu-alloy powder exhibits improved sphericity, with a visible reduction in agglomerations/satellites relative to the used powder.
  • the plasma processing avoids a full remelting of the used powder, avoiding coarsening and heterogeneity of the micro structure.
  • the micro structure of the Cu-alloy powder is substantially homogenous.
  • FIG. 5 illustrates cross-sectional back-scattered electron detector (BSE) images comparing example used particles and a recycled Cu-alloy powder processed according to some embodiments described herein.
  • the samples were polished and etched with FeCh solution to reveal intermetallic structure.
  • comparable intermetallic size/spacing can be seen in both the used powder and the recycled Cu-alloy powder.
  • FIG. 6 illustrates an example x-ray powder diffraction (XRD) plot comparing example used particles and a recycled Cu-alloy powder processed according to some embodiments described herein. As illustrated, XRD analysis did not detect any significant phase changes in the processed powder, indicating no significant microstructural changes. Furthermore, both XRD spectra show Cu reflections and low-intensity reflection for CnNb intermetallic.
  • the microwave plasma processing embodiments herein are capable of recycling used Cu-alloy powder to produce a recycled powder having improved sphericity, while maintaining the bulk chemistry and intermetallic size/spacing, while reducing oxygen content to at or below about 600 wt. ppm. Additional Embodiments
  • conditional language used herein such as, among others, “can,” “could,” “might,” “may,” “e.g.,” and the like, unless specifically stated otherwise, or otherwise understood within the context as used, is generally intended to convey that certain embodiments include, while other embodiments do not include, certain features, elements and/or steps. Thus, such conditional language is not generally intended to imply that features, elements and/or steps are in any way required for one or more embodiments or that one or more embodiments necessarily include logic for deciding, with or without author input or prompting, whether these features, elements and/or steps are included or are to be performed in any particular embodiment.
  • the methods disclosed herein may include certain actions taken by a practitioner; however, the methods can also include any third-party instruction of those actions, either expressly or by implication.
  • the ranges disclosed herein also encompass any and all overlap, sub-ranges, and combinations thereof.
  • Language such as “up to,” “at least,” “greater than,” “less than,” “between,” and the like includes the number recited. Numbers preceded by a term such as “about” or “approximately” include the recited numbers and should be interpreted based on the circumstances (e.g., as accurate as reasonably possible under the circumstances, for example ⁇ 5%, ⁇ 10%, ⁇ 15%, etc.).
  • a phrase referring to “at least one of’ a list of items refers to any combination of those items, including single members.
  • “at least one of: A, B, or C” is intended to cover: A, B, C, A and B, A and C, B and C, and A, B, and C.
  • Conjunctive language such as the phrase “at least one of X, Y and Z,” unless specifically stated otherwise, is otherwise understood with the context as used in general to convey that an item, term, etc. may be at least one of X, Y or Z.

Abstract

Les modes de réalisation de la présente invention concernent des systèmes et des procédés de fabrication de particules de poudre d'alliage de cuivre recyclées à partir de particules de poudre d'alliage de cuivre usagées ou déficientes. Dans certains modes de réalisation, des particules de poudre d'alliage de cuivre usagées comprenant de l'oxygène proche de la surface sont introduites dans une torche à plasma micro-onde. Dans certains modes de réalisation, les particules de poudre d'alliage de cuivre usagées sont chauffées à l'intérieur de la torche à plasma micro-onde pour éliminer au moins partiellement l'oxygène et former des particules de poudre d'alliage de cuivre recyclées, sans faire fondre les particules de poudre d'alliage de cuivre usagées.
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